EP0197657B1 - A novel process for preparing amides from nitriles and amines - Google Patents
A novel process for preparing amides from nitriles and amines Download PDFInfo
- Publication number
- EP0197657B1 EP0197657B1 EP86301647A EP86301647A EP0197657B1 EP 0197657 B1 EP0197657 B1 EP 0197657B1 EP 86301647 A EP86301647 A EP 86301647A EP 86301647 A EP86301647 A EP 86301647A EP 0197657 B1 EP0197657 B1 EP 0197657B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- process according
- group
- formula
- carbonitrile
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- 150000001412 amines Chemical class 0.000 title claims description 22
- 150000002825 nitriles Chemical class 0.000 title claims description 21
- 150000001408 amides Chemical class 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title description 7
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 21
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 19
- 239000000376 reactant Substances 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- LELOWRISYMNNSU-UHFFFAOYSA-N Hydrocyanic acid Natural products N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000005842 heteroatom Chemical group 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 125000003341 7 membered heterocyclic group Chemical group 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000010948 rhodium Substances 0.000 claims description 8
- 150000004985 diamines Chemical class 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000000304 alkynyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- GYLDXXLJMRTVSS-UHFFFAOYSA-N n-butylacetamide Chemical group CCCCNC(C)=O GYLDXXLJMRTVSS-UHFFFAOYSA-N 0.000 claims description 5
- -1 pryidine Chemical compound 0.000 claims description 5
- 125000000520 N-substituted aminocarbonyl group Chemical group [*]NC(=O)* 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 150000003335 secondary amines Chemical class 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000004450 alkenylene group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000005263 alkylenediamine group Chemical group 0.000 claims description 2
- 125000004419 alkynylene group Chemical group 0.000 claims description 2
- 125000000732 arylene group Chemical group 0.000 claims description 2
- 150000003857 carboxamides Chemical class 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 150000003141 primary amines Chemical class 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012327 Ruthenium complex Substances 0.000 claims 1
- MLIYPCQSOXNTLJ-UHFFFAOYSA-N carbon monoxide;ruthenium dihydride;triphenylphosphane Chemical compound [RuH2].[O+]#[C-].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 MLIYPCQSOXNTLJ-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 18
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 14
- 239000004952 Polyamide Substances 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 14
- 229920002647 polyamide Polymers 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 12
- RXFATFKBDIQXLS-UHFFFAOYSA-N ruthenium dihydride;triphenylphosphane Chemical compound [RuH2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RXFATFKBDIQXLS-UHFFFAOYSA-N 0.000 description 12
- 238000001228 spectrum Methods 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 230000009102 absorption Effects 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 125000005219 aminonitrile group Chemical group 0.000 description 8
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 7
- 235000019253 formic acid Nutrition 0.000 description 7
- 229920002302 Nylon 6,6 Polymers 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- PRZSXZWFJHEZBJ-UHFFFAOYSA-N thymol blue Chemical compound C1=C(O)C(C(C)C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C(=CC(O)=C(C(C)C)C=2)C)=C1C PRZSXZWFJHEZBJ-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 229920000299 Nylon 12 Polymers 0.000 description 2
- 229920003188 Nylon 3 Polymers 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002751 molybdenum Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003304 ruthenium compounds Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- IHXNSHZBFXGOJM-HWKANZROSA-N (e)-2-methylbut-2-enenitrile Chemical compound C\C=C(/C)C#N IHXNSHZBFXGOJM-HWKANZROSA-N 0.000 description 1
- ZWKNLRXFUTWSOY-QPJJXVBHSA-N (e)-3-phenylprop-2-enenitrile Chemical compound N#C\C=C\C1=CC=CC=C1 ZWKNLRXFUTWSOY-QPJJXVBHSA-N 0.000 description 1
- ISBHMJZRKAFTGE-ONEGZZNKSA-N (e)-pent-2-enenitrile Chemical compound CC\C=C\C#N ISBHMJZRKAFTGE-ONEGZZNKSA-N 0.000 description 1
- UVKXJAUUKPDDNW-NSCUHMNNSA-N (e)-pent-3-enenitrile Chemical compound C\C=C\CC#N UVKXJAUUKPDDNW-NSCUHMNNSA-N 0.000 description 1
- ZIRGWUZHKJDYKT-UHFFFAOYSA-N 1,3-thiazole-2-carbonitrile Chemical compound N#CC1=NC=CS1 ZIRGWUZHKJDYKT-UHFFFAOYSA-N 0.000 description 1
- HFZZTHJMXZSGFP-UHFFFAOYSA-N 1-benzofuran-2-amine Chemical compound C1=CC=C2OC(N)=CC2=C1 HFZZTHJMXZSGFP-UHFFFAOYSA-N 0.000 description 1
- OMMWHZACYMWERD-UHFFFAOYSA-N 11-aminoundecanenitrile Chemical compound NCCCCCCCCCCC#N OMMWHZACYMWERD-UHFFFAOYSA-N 0.000 description 1
- QKPVEISEHYYHRH-UHFFFAOYSA-N 2-methoxyacetonitrile Chemical compound COCC#N QKPVEISEHYYHRH-UHFFFAOYSA-N 0.000 description 1
- XXUNIGZDNWWYED-UHFFFAOYSA-N 2-methylbenzamide Chemical compound CC1=CC=CC=C1C(N)=O XXUNIGZDNWWYED-UHFFFAOYSA-N 0.000 description 1
- NWPNXBQSRGKSJB-UHFFFAOYSA-N 2-methylbenzonitrile Chemical compound CC1=CC=CC=C1C#N NWPNXBQSRGKSJB-UHFFFAOYSA-N 0.000 description 1
- FPPLREPCQJZDAQ-UHFFFAOYSA-N 2-methylpentanedinitrile Chemical compound N#CC(C)CCC#N FPPLREPCQJZDAQ-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- CFEYBLWMNFZOPB-UHFFFAOYSA-N Allylacetonitrile Natural products C=CCCC#N CFEYBLWMNFZOPB-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229910017333 Mo(CO)6 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- UAMZETBJZRERCQ-UHFFFAOYSA-N alpha-aminopropionitrile Chemical compound CC(N)C#N UAMZETBJZRERCQ-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- BHXFKXOIODIUJO-UHFFFAOYSA-N benzene-1,4-dicarbonitrile Chemical compound N#CC1=CC=C(C#N)C=C1 BHXFKXOIODIUJO-UHFFFAOYSA-N 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- VBWIZSYFQSOUFQ-UHFFFAOYSA-N cyclohexanecarbonitrile Chemical compound N#CC1CCCCC1 VBWIZSYFQSOUFQ-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229960002523 mercuric chloride Drugs 0.000 description 1
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- PVCOXMQIAVGPJN-UHFFFAOYSA-N piperazine-1,4-diamine Chemical class NN1CCN(N)CC1 PVCOXMQIAVGPJN-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
- C07D295/182—Radicals derived from carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
Definitions
- This invention relates to the preparation of amides from nitriles and amines of polyamides directly from dinitriles and diamines or from aminonitriles.
- amide compounds including polyamides have so far been developed and used in various industrial fields. These are particularly, but not exclusively, useful as materials for synthetic fibres and plastics moulds, dyeability improvers or antistatic agents for such items, finishing or sizing agents for yarns and textiles, surfactants, coagulants, adhesives, organic solvents, plastics-foaming agents, printing-ink additives, dyestuffs, organic pigments, pharmaceuticals, agricultural chemicals, livestock feeds, and intermediate compounds for preparing such materials.
- Two US Patent Specifications and one European Patent Specification are particular examples of the synthesis of amides from a nitrile and an amine in the presence of water.
- US-A-3 825 596 discloses a process for preparing N,N-dialkyl toluamide by reacting tolunitrile with a di- or trialkylamine and water under heated, preferably pressurised conditions, optionally in the presence of a catalyst.
- Suggested and tried catalysts include zinc chloride, mercuric chloride, cadmium acetate, lead acetate, zinc acetate, copper acetate, cobalt acetate and nickel acetate.
- US-A-4 380 623 discloses a process for preparing amides comprising reacting a nitrile, an amine and water in the presence of a carbon dioxide catalyst.
- the preparation of nylon-6,6 is described by reacting adiponitrile, hexamethylene diamine and water in the presence of CO2.
- EP-A-0 070 424 discloses a process for preparing amides from nitriles and amines in the presence of water and a catalyst at a temperature between 80 and 220°C.
- the catalyst in this case is a copper derivative which may also contain chromium, molybdenum, vanadium, manganese or zinc.
- the present invention provides a process for the preparation of organic amides by reaction of a carbonitrile and a primary or secondary amine in which the carbonitrile is reacted directly with an equivalent amount of the primary or secondary amine, the reaction taking place by heating the reactants in the presence of at least a stoichiometric amount of water relative to the carbonitrile reactant, and in the presence of a catalyst comprising a complex containing one or more of ruthenium, rhodium, and molybdenum.
- This process has a minimum number of steps, so that reaction time is shorter, equipment more compact and operation cleaner.
- the invention develops the abovementioned direct synthesis of amides into synthesis of polyamides with similar advantages.
- carbonitrile or"nitrile means an organic compound having at least one cyano group in its molecule
- amine an organic compound having at least one amino group. Both the cyano group and the amino group may be contained in one molecule, in which case they constitute an aminonitrile compound.
- amide means an organic compound having at least one amide linkage in its molecule, including a so-called polyamide.
- the present invention includes the following three principal and preferred embodiments.
- the nitrile is represented by the general formula R1CN where R1 denotes (i) an alkyl, alkenyl, alkynyl, cycloalkyl or aryl group of up to 20 carbon atoms, or (ii) a univalent residue of a 3 to 7 membered heterocyclic group having in the ring up to 3 hetero atoms each of which is O, N or S, with the proviso that the groups defined for R1 optionally contain one or more of the following substituents: an aryl, alkenyl or alkynyl group of up to 12 carbon atoms, a univalent residue of a 3 to 7 membered heterocyclic group containing up to 3 hetero atoms each of which is O, N or S, or an OR, CO2R, NR2, SR, SiR3 or CONR2 group where R is an optionally substituted alkyl group containing up to 10 carbon atoms or a phenyl group; and
- the carbonitrile reactant is a dinitrile of the formula R4(CN)2 where R4 denotes (i) an alkylene, alkenylene, alkynylene, cycloalkylene or arylene group having up to 20 carbon atoms; (ii) a bivalent residue of a 3 to 7 membered heterocyclic group having in the ring up to 3 hetero atoms each of which is O, N or S; or (iii) a group consisting of two aliphatic hydrocarbon residues each having up to 10 carbon atoms bridged by phenylene group, an O, N or S hetero atom, or a bivalent residue of a 3 to 7 membered heterocyclic group having in the ring up to 3 hetero atoms each of which is O, N or S; with the proviso that any of such groups optionally contain one or more of the following substituents: an aryl, alkenyl or alkynyl group of up to 12 carbon atom
- the product is a polyamide having a recurring unit represented by the following general formula:
- both the carbonitrile and the amine reactant are the same or different aminonitriles of the formula HN(R5)_R6_CN where R5 and R6 are as defined as above.
- the product is a polyamide having recurring units of the formula
- the repeating units in the polyamide may or may not be the same.
- nitriles for use in the first embodiment include acetonitrile, propionitrile, butyronitrile, acrylonitrile, methacrylonitrile, 2-methyl-2-butenenitrile, 2-pentenenitrile, 3-pentenenitrile, cinnamonitrile, cyclohexanecarbonitrile, benzonitrile, 2-thiazolecarbonitrile and methoxyacetonitrile.
- the reacting amine is a monoamine
- nitriles having two or more cyano groups such as 1,4-dicyanobutane, 1,6-dicyclohexane and methylglutaronitrile may be included in the first embodiment.
- amines for use in the first embodiment include methylamine, ethylamine, butylamine, diethylamine, benzylamine, benzylmethylamine, cyclohexylamine, aniline, 2-benzofuranamine, anisidine, pyrrolidine, piperidine and morpholine.
- amines having two or more amine groups e.g. hexamethylenediamine, 1,2-diaminocyclohexane, diaminopiperazines, and bis-hexamethylenetriamines may be used in the first embodiment.
- dinitriles are alkylenedinitriles having the general formula NC(CH2) n CN where n is an integer of 1-20
- preferable diamines are alkylenediamines having the general formula HN(R5)_(CH2)m-NHR7 where m is an integer of 1-20
- polyamides having a recurring unit represented by the general formula: where R5 and R7 are as defined above.
- preferable aminonitriles are aminoalkylnitriles having the general formula NC(CH2) p NHR5 where p is an integer of 1-3 or 5-20, from which will result polyamides having a recurring unit represented by the general formula: where R5 is as defined above.
- two or more dinitriles and/or diamines and two or more aminonitriles may be used and in these cases copolyamides will be obtained.
- nitriles and/or amines and aminonitriles that are trifunctional or polyfunctional also can be added in such a manner that nearly stoichiometric proportions as a whole are attained, if required, in order to improve the properties of the resulting polyamides.
- a small amount of monoamine, mononitrile or monocarboxylic acid may be added to the reaction mixture as a polymerization inhibitor in the second and third embodiments of the invention, in order to control the polymer viscosity.
- Catalysts preferred in the process of the present invention are the ruthenium complexes RuH2(PPh3)4 and RuH2(CO)(PPh2)3, the molybdenum complex Mo(CO)6 and the rhodium complex Rh(CO)(OH)(PPh3), which have high activity.
- catalysts may be used alone or in combination and, if required, along with an appropriate promoter such as a metal hydroxide.
- a catalytic amount is normally required, e.g. 0.001 to 10 mol %, preferably 0.1 to 3 mol %, based on the starting nitrile, although the reaction can be effected with smaller or larger amounts.
- reaction it is preferred for the reaction to be carried out in an inert gas. Although the reaction readily proceeds on addition of only the catalyst to amines, nitriles (or aminonitriles) and water, it will be carried out more effectively in the presence of a water-miscible organic solvent such as 1,2-dimethoxyethane, dioxane, pyridine, diglyme or tetrahydrofuran. Though the reaction temperature has no specified upper limit, not higher than 250°C is preferable. The reaction pressure may be atmospheric or higher, if required. The amount of water required is at least one equivalent relative to the nitrile reactant. In general, however, a stoichiometric excess of water will be present, e.g. in the range 1-100 equivalents of water, preferably 1-3 equivalents, relative to the nitrile.
- a stoichiometric excess of water will be present, e.g. in the range 1-100 equivalents of water, preferably 1-3 equivalents, relative to the
- a magnetic stirrer was put into a test tube of 30-ml capacity, and argon gas was admitted to displace the air.
- Acetonitrile 2.0 mmol
- butylamine 2.2 mmol
- water 4.0 mmol
- RuH2(PPh3)4 0.06 mmol
- DME 1,2-dimethoxyethane
- N-butylacetamide was obtained in a 93% yield. Identification of N-butylacetamide was conducted by means IR, NMR and mass spectrum data.
- Example 2 The catalyst RuH2(PPh3)4 used in the reaction in Example 1 was replaced by the under-mentioned 22 compounds and respective series of the reaction were carried out to obtain N-butylacetamide in yields and with the acetonitrile conversions respectively given in Table 2 below. It will be seen that catalysts in accordance with the invention (Examples 24 to 27 and 31) are superior in yield and/or conversion to most of the comparative Examples 28 to 30 and 32 to 45.
- Adiponitrile (0.216 g), hexamethylenediamine (0.232 g), RuH2(PPh3)4 (0.069 g), water (0.072 g) and 1,2-dimethoxyethane (0.5 ml) were reacted in an argon gas atmosphere in a sealed tube under the same conditions as Example 1. After the reaction, precipitates were separated by filtration, washed with chloroform and dried. Then, nylon-66 was obtained in a 92% yield.
- nylon-66 Its number average molecular weight was 4,100 which was calculated from terminal amino-groups quantified by p-toluene sulfonic acid using thymol blue as an indicator
- Adiponitrile (0.216 g), hexamethylenediamine (0.232 g), RuH2(PPh3)4 (0.069 g), water (0.072 g) and 1,2-dimethoxyethane (0.5 ml) were reacted at 200°C in an argon gas atmosphere for 24 hours in a sealed tube. After the reaction, precipitates were separated by filtration, washed with chloroform and dried. Then, nylon-66 having a melting point temperature higher than 255°C was obtained in a 98% yield. Its infrared and ⁇ H NMR spectra similar to those in Example 46 resulted. The number average molecular weight was 8,900 which was calculated from terminal amino groups quantified by p-toluene sulfonic acid using thymol blue as an indicator (with respect to the polymer solution in cresol).
- Adiponitrile (0.216 g), ethylenediamine (0.120 g), RuH2(PPh3)4 (0.069 g), water (0.072 g) and 1,2-dimethoxyethane (0.5 ml) were reacted in a sealed tube under the same conditions as Example 1. After the reaction, precipitates were separated by filtration, washed with chloroform and dried. Then, nylon-2,6 was obtained in a 99% yield. Its number average molecular weight was 3,700 which was calculated from terminal amino groups quantified by p-toluene sulfonic acid using thymol blue as an indicator.
- Adiponitrile (0.216 g), 1,4-cyclohexanediamine (0.228 g), RuH2(PPh3)4 (0.069 g), water (0.074 g) and 1,2-dimethoxyethane (0.5 ml) were reacted at 180°C in an argon gas atmosphere for 24 hours in a sealed tube. After the reaction, precipitates were separated by filtration washed with chloroform and dried. Then, polyamide having a decomposition temperature of 208°C was obtained in a 98% yield. Its number average molecular weight was 1,000 which was calculated in the same manner as described in Example 48.
- Adiponitrile (0.216 g), piperazine (0.172 g), RuH2(PPh3)4 (0.069 g), water (0.077 g) and 1,2-dimethoxyethane (0.5 ml) were reacted at 180°C in an argon gas atmosphere for 24 hours in a sealed tube. After the reaction, precipitates were separated by filtration, washed with chloroform and dried. Then, polyamide having a decomposition temperature of 230°C was obtained in a 98% yield. Its number average molecular weight was 2,200 which was calculated in the same manner as described in Example 48.
- 1,4-Phenylenediacetonitri1e 0.312 g
- hexamethylenediamine (0.232 g)
- RuH2(PPh3)4 0.069 g
- water 0.074 g
- 1,2-dimethoxyethane 0.5 ml
- precipitates were separated by filtration, washed with chloroform and dried.
- a polyamide that did not melt at 300°C was obtained in a 93% yield. Its number average molecular weight was 14,000, which was calculated in the same manner as described in Example 48.
- the use of ruthenium, rhodium and molybdenum complexes according to the present invention enables amides to be efficiently prepared directly from nitriles, amines and water, in a single-step process, so that curtailment of reaction time, compaction of equipments and clean operations can be realised as compared with the conventional two-step process for amide synthesis.
- the advantage of the present invention lies in the fact that the reaction can be effected under neutral conditions with a small amount of water, which is economical in energy.
- dinitriles and diamines, or aminonitriles according to the present invention polyamides can be produced in a single-step manufacturing process.
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Description
- This invention relates to the preparation of amides from nitriles and amines of polyamides directly from dinitriles and diamines or from aminonitriles.
- Many kinds of amide compounds including polyamides have so far been developed and used in various industrial fields. These are particularly, but not exclusively, useful as materials for synthetic fibres and plastics moulds, dyeability improvers or antistatic agents for such items, finishing or sizing agents for yarns and textiles, surfactants, coagulants, adhesives, organic solvents, plastics-foaming agents, printing-ink additives, dyestuffs, organic pigments, pharmaceuticals, agricultural chemicals, livestock feeds, and intermediate compounds for preparing such materials.
- Hitherto, when an amide has been synthesized from a nitrile and an amine, usually the nitrile is hydrolysed and thereby converted into carboxylic acid which is subsequently condensed with the amine.
- Two US Patent Specifications and one European Patent Specification are particular examples of the synthesis of amides from a nitrile and an amine in the presence of water.
- Thus US-A-3 825 596 discloses a process for preparing N,N-dialkyl toluamide by reacting tolunitrile with a di- or trialkylamine and water under heated, preferably pressurised conditions, optionally in the presence of a catalyst. Suggested and tried catalysts include zinc chloride, mercuric chloride, cadmium acetate, lead acetate, zinc acetate, copper acetate, cobalt acetate and nickel acetate.
- US-A-4 380 623 discloses a process for preparing amides comprising reacting a nitrile, an amine and water in the presence of a carbon dioxide catalyst. In particular, the preparation of nylon-6,6 is described by reacting adiponitrile, hexamethylene diamine and water in the presence of CO₂.
- EP-A-0 070 424 discloses a process for preparing amides from nitriles and amines in the presence of water and a catalyst at a temperature between 80 and 220°C. The catalyst in this case is a copper derivative which may also contain chromium, molybdenum, vanadium, manganese or zinc.
- However, conventional manufacturing processes result in various problems. These are related inter alia to increase of process steps, separation of products in each step, equipment for preventing pollution caused by by-products, and the cost of production.
- The present invention provides a process for the preparation of organic amides by reaction of a carbonitrile and a primary or secondary amine in which the carbonitrile is reacted directly with an equivalent amount of the primary or secondary amine, the reaction taking place by heating the reactants in the presence of at least a stoichiometric amount of water relative to the carbonitrile reactant, and in the presence of a catalyst comprising a complex containing one or more of ruthenium, rhodium, and molybdenum. This process has a minimum number of steps, so that reaction time is shorter, equipment more compact and operation cleaner.
- In one of its embodiments the invention develops the abovementioned direct synthesis of amides into synthesis of polyamides with similar advantages.
- In this specification, the term "carbonitrile" or"nitrile" means an organic compound having at least one cyano group in its molecule, and the term "amine" an organic compound having at least one amino group. Both the cyano group and the amino group may be contained in one molecule, in which case they constitute an aminonitrile compound. Further, the term "amide" means an organic compound having at least one amide linkage in its molecule, including a so-called polyamide.
- The present invention includes the following three principal and preferred embodiments.
- In the first preferred embodiment of the invention, the nitrile is represented by the general formula R¹CN where R¹ denotes (i) an alkyl, alkenyl, alkynyl, cycloalkyl or aryl group of up to 20 carbon atoms, or (ii) a univalent residue of a 3 to 7 membered heterocyclic group having in the ring up to 3 hetero atoms each of which is O, N or S, with the proviso that the groups defined for R¹ optionally contain one or more of the following substituents: an aryl, alkenyl or alkynyl group of up to 12 carbon atoms, a univalent residue of a 3 to 7 membered heterocyclic group containing up to 3 hetero atoms each of which is O, N or S, or an OR, CO₂R, NR₂, SR, SiR₃ or CONR₂ group where R is an optionally substituted alkyl group containing up to 10 carbon atoms or a phenyl group; and the amine reactant is of the formula R²R³NH where each of R² and R³ represents a hydrogen atom or a group as defined for R¹, or _NR²R³ is a saturated or unsaturated heterocyclic ring optionally containing O, S or another N as hetero atom. In such a case the amide product may be represented by the formula R¹_CO_NR²R³ where R¹, R² and R³ are as defined above.
- In the second principal embodiment of the invention, the carbonitrile reactant is a dinitrile of the formula R⁴(CN)₂ where R⁴ denotes (i) an alkylene, alkenylene, alkynylene, cycloalkylene or arylene group having up to 20 carbon atoms; (ii) a bivalent residue of a 3 to 7 membered heterocyclic group having in the ring up to 3 hetero atoms each of which is O, N or S; or (iii) a group consisting of two aliphatic hydrocarbon residues each having up to 10 carbon atoms bridged by phenylene group, an O, N or S hetero atom, or a bivalent residue of a 3 to 7 membered heterocyclic group having in the ring up to 3 hetero atoms each of which is O, N or S; with the proviso that any of such groups optionally contain one or more of the following substituents: an aryl, alkenyl or alkynyl group of up to 12 carbon atoms, a univalent residue of a 3 to 7 membered heterocyclic group containing up to 3 hetero atoms each of which is O, N or S, or an OR, CO₂R, NR₂, SR, SiR₃ or CONR₂ group where R is an optionally substituted alkyl group containing up to 10 carbon atoms or a phenyl group; and the amine is a diamine of the formula HN(R⁵) _ R⁶ _ (R⁷)NH where each of R⁵ and R⁷ represents a hydrogen atom or a group as defined for R¹, and R⁶ is a group as defined for R⁴.
-
-
- Depending upon whether the same or two different aminonitriles are used as the nitrile and amine reactants, the repeating units in the polyamide may or may not be the same.
- Examples of nitriles for use in the first embodiment include acetonitrile, propionitrile, butyronitrile, acrylonitrile, methacrylonitrile, 2-methyl-2-butenenitrile, 2-pentenenitrile, 3-pentenenitrile, cinnamonitrile, cyclohexanecarbonitrile, benzonitrile, 2-thiazolecarbonitrile and methoxyacetonitrile. Further, when the reacting amine is a monoamine, nitriles having two or more cyano groups, such as 1,4-dicyanobutane, 1,6-dicyclohexane and methylglutaronitrile may be included in the first embodiment.
- Examples of amines for use in the first embodiment include methylamine, ethylamine, butylamine, diethylamine, benzylamine, benzylmethylamine, cyclohexylamine, aniline, 2-benzofuranamine, anisidine, pyrrolidine, piperidine and morpholine. Further, when the reacting nitrile is a mononitrile, amines having two or more amine groups, e.g. hexamethylenediamine, 1,2-diaminocyclohexane, diaminopiperazines, and bis-hexamethylenetriamines may be used in the first embodiment.
- In the second embodiment, preferably dinitriles are alkylenedinitriles having the general formula NC(CH₂)nCN where n is an integer of 1-20, while preferable diamines are alkylenediamines having the general formula HN(R⁵)_(CH₂)m-NHR⁷ where m is an integer of 1-20, and from those reactants are obtained polyamides having a recurring unit represented by the general formula:
where R⁵ and R⁷ are as defined above. -
- In the second and third embodiments, two or more dinitriles and/or diamines and two or more aminonitriles may be used and in these cases copolyamides will be obtained. Moreover, nitriles and/or amines and aminonitriles that are trifunctional or polyfunctional also can be added in such a manner that nearly stoichiometric proportions as a whole are attained, if required, in order to improve the properties of the resulting polyamides.
- A small amount of monoamine, mononitrile or monocarboxylic acid may be added to the reaction mixture as a polymerization inhibitor in the second and third embodiments of the invention, in order to control the polymer viscosity.
- Catalysts preferred in the process of the present invention are the ruthenium complexes RuH₂(PPh₃)₄ and RuH₂(CO)(PPh₂)₃, the molybdenum complex Mo(CO)₆ and the rhodium complex Rh(CO)(OH)(PPh₃), which have high activity.
- These catalysts may be used alone or in combination and, if required, along with an appropriate promoter such as a metal hydroxide.
- Only a catalytic amount is normally required, e.g. 0.001 to 10 mol %, preferably 0.1 to 3 mol %, based on the starting nitrile, although the reaction can be effected with smaller or larger amounts.
- It is preferred for the reaction to be carried out in an inert gas. Although the reaction readily proceeds on addition of only the catalyst to amines, nitriles (or aminonitriles) and water, it will be carried out more effectively in the presence of a water-miscible organic solvent such as 1,2-dimethoxyethane, dioxane, pyridine, diglyme or tetrahydrofuran. Though the reaction temperature has no specified upper limit, not higher than 250°C is preferable. The reaction pressure may be atmospheric or higher, if required. The amount of water required is at least one equivalent relative to the nitrile reactant. In general, however, a stoichiometric excess of water will be present, e.g. in the range 1-100 equivalents of water, preferably 1-3 equivalents, relative to the nitrile.
- Some of the preferred embodiments of the present invention will be illustrated by way of the following examples.
- A magnetic stirrer was put into a test tube of 30-ml capacity, and argon gas was admitted to displace the air. Acetonitrile (2.0 mmol), butylamine (2.2 mmol), water (4.0 mmol), RuH₂(PPh₃)₄ (0.06 mmol) and 1,2-dimethoxyethane (DME, 0.5 ml) were placed in the test tube, which was thereafter sealed.
- The solution was allowed to react to 160°C for 24 hours while stirring. After cooling to _78°C, the sealed tube was opened and the product was isolated by passing through a short Florisil (Registered Trade Mark) column. N-butylacetamide was obtained in a 93% yield. Identification of N-butylacetamide was conducted by means IR, NMR and mass spectrum data.
-
- Although a ruthenium compound was used as the catalyst in Examples enumerated above, it was confirmed that amides were also obtainable using rhodium and molybdenum complexes in lieu of the ruthenium compound.
- The catalyst RuH₂(PPh₃)₄ used in the reaction in Example 1 was replaced by the under-mentioned 22 compounds and respective series of the reaction were carried out to obtain N-butylacetamide in yields and with the acetonitrile conversions respectively given in Table 2 below. It will be seen that catalysts in accordance with the invention (Examples 24 to 27 and 31) are superior in yield and/or conversion to most of the comparative Examples 28 to 30 and 32 to 45.
- Adiponitrile (0.216 g), hexamethylenediamine (0.232 g), RuH₂(PPh₃)₄ (0.069 g), water (0.072 g) and 1,2-dimethoxyethane (0.5 mℓ) were reacted in an argon gas atmosphere in a sealed tube under the same conditions as Example 1. After the reaction, precipitates were separated by filtration, washed with chloroform and dried. Then, nylon-66 was obtained in a 92% yield. Its number average molecular weight was 4,100 which was calculated from terminal amino-groups quantified by p-toluene sulfonic acid using thymol blue as an indicator The nylon-66 was identified by IR (KBr) spectrum which showed absorptions at 3,230 (N_H, m), 2,910 (C_H, s), 2,840 (s), 1,630 (C=O, s), 1,530 (N_H, s), 1,225 (w) and 740 (w) cm_1; and by ʹHNMR spectrum (HCO₂H, 60MHz): δ 0.93-1.85 (m, 12H, _CH₂_), 1.95-2.60 (m, 4H, _COH₂_), 2,82-3.43 (m, 4H, _N_CH₂_) and 8.45 (br.s, 2H, _NH).
- Adiponitrile (0.216 g), hexamethylenediamine (0.232 g), RuH₂(PPh₃)₄ (0.069 g), water (0.072 g) and 1,2-dimethoxyethane (0.5 mℓ) were reacted at 200°C in an argon gas atmosphere for 24 hours in a sealed tube. After the reaction, precipitates were separated by filtration, washed with chloroform and dried. Then, nylon-66 having a melting point temperature higher than 255°C was obtained in a 98% yield. Its infrared and ʹH NMR spectra similar to those in Example 46 resulted. The number average molecular weight was 8,900 which was calculated from terminal amino groups quantified by p-toluene sulfonic acid using thymol blue as an indicator (with respect to the polymer solution in cresol).
- Adiponitrile (0.216 g), ethylenediamine (0.120 g), RuH₂(PPh₃)₄ (0.069 g), water (0.072 g) and 1,2-dimethoxyethane (0.5 mℓ) were reacted in a sealed tube under the same conditions as Example 1. After the reaction, precipitates were separated by filtration, washed with chloroform and dried. Then, nylon-2,6 was obtained in a 99% yield. Its number average molecular weight was 3,700 which was calculated from terminal amino groups quantified by p-toluene sulfonic acid using thymol blue as an indicator. Its infrared (KBr) spectrum showed absorptions at 3,350 (N_H, s), 3,170 (N_H, s), 2,950 (C_H, s), 1,645 (C=O, s), 1,545 (N_H, m), 1,330 (m), 1,120 (m) and 800 (m) cm_1; and ʹH NMR spectrum (HCO₂H, 60MHz): δ 1.03-1.96 (m, 4H, _CH₂_), 1.96-2.68 (m, 4H, _COCH₂_), 3.05-3.95 (m, 4H, _N-CH₂_) and 8.22 (br.s, 2H, _NH).
- 2-aminopropionitrile (0.282 g), water (0.145 g), RuH₂(PPh₃)₄ (0.069 g) and 1,2-dimethoxyethane (0.5 mℓ) were reacted at 200°C in an argon gas atmosphere for 24 hours in a sealed tube. After the reaction, precipitates were separated by filtration, washed with chloroform and dried. Then, nylon-3 was obtained in a 98% yield. Its number average molecular weight was 1,600 which was calculated in the same manner as described in Example 48. Its infrared (KBr) spectrum showed absorptions at 3,290 (N_H, s), 2,940 (C_H, w), 1,640 (C=O, s), 1,545 (N_H, s), 1,435 (m), 1,115 (m) and 695 (m) cm_1; and ʹHNMR spectrum (HCO₂H, 60MHz): δ 1.78-2.98 (m, 2H, _COCH₂_), 3.05-4.14 (m, 2H, N_CH₂_) and 7.56 (br.s, 1H, _NH).
- 11-Aminoundecanenitrile (0.393 g), water (0.072 g), RuH₂(PPh₃)₄ (0.069 g) and 1,2-dimethoxyethane (0.5 mℓ) were reacted in an argon gas atmosphere in a sealed tube under the same conditions as Example 1. After the reaction, precipitates were separated by filtration, washed with chloroform and dried. Then, nylon-12 was obtained in a 99% yield. Its number average molecular weight was 5,000 which was calculated in the same manner as described in Example 48. Its infrared (KBr) spectrum showed absorptions at 3,290 (N_H, s), 2,940 (C_H, w), 1,640 (C=O, s), 1,545 (N_H, s), 1,435 (m), 1,115 (m) and 695 (m) cm_1; and ʹH NMR (HCO₂H, 60MHz): δ 0.93-1.85 (m, 18H, _CH₂_), 1.95-2.60 (m, 2H, _COCH₂_), 2.82-3.43 (m, 2H, _N-CH₂_) and 8.45 (br.s, 2H, _NH).
- Terephthalonitrile (0.256 g), hexamethylenediamine (0.232 g), RuH₂(PPh₃)₄ (0.069 g), water (0.074 g) and 1,2-dimethoxyethane (0.5 ml) were reacted at 180°C in an argon gas atmosphere for 24 hours in a sealed tube. After the reaction, precipitates were separated by filtration, washed with chloroform and dried. Then, polyhexamethyleneterephthalamide having a decomposition temperature of 265°C was obtained in a 98% yield. Its number average molecular weight was 1,200 which was calculated in the same manner as described in Example 48., Its infrared (KBr) spectrum showed absorptions at 3,160 (N_H, s), 3,070 (C_H, m), 2,920 (C_H, s), 2,860 (C_H, m), 1,620 (C=O, s), 1,535 (N_H, m), 1,410 (m), 1,285 (m) and 860 (m) cm_1; and ʹH NMR (HCO₂H, 60MHz): δ 0.71-2.34 (m, 8H, _CH₂_), 2.90-3.76 (m, 4H, _NCH₂), 6.21 (br.s, 2H, NH) and 7.00-7.54 (m, 4H, ArH).
- Adiponitrile (0.216 g), 1,4-cyclohexanediamine (0.228 g), RuH₂(PPh₃)₄ (0.069 g), water (0.074 g) and 1,2-dimethoxyethane (0.5 mℓ) were reacted at 180°C in an argon gas atmosphere for 24 hours in a sealed tube. After the reaction, precipitates were separated by filtration washed with chloroform and dried. Then, polyamide having a decomposition temperature of 208°C was obtained in a 98% yield. Its number average molecular weight was 1,000 which was calculated in the same manner as described in Example 48. Its infrared (KBr) spectrum showed absorptions at 3,180 (N_H, s), 2,925 (C_H, s), 2,860 (C_H, m), 1,630 (C=O, s), 1,540 (N_H, s), 1,410 (m), 1,115 (m) and 745 (m) cm_1; and ʹH NMR (HCO₂H, 60mHz): δ 0.84-1.97 (m, 16H), 2.70-3.27 (m, 2H, _NCHʹ-) and 6.76 (br.s, 2H, NH).
- Adiponitrile (0.216 g), piperazine (0.172 g), RuH₂(PPh₃)₄ (0.069 g), water (0.077 g) and 1,2-dimethoxyethane (0.5 mℓ) were reacted at 180°C in an argon gas atmosphere for 24 hours in a sealed tube. After the reaction, precipitates were separated by filtration, washed with chloroform and dried. Then, polyamide having a decomposition temperature of 230°C was obtained in a 98% yield. Its number average molecular weight was 2,200 which was calculated in the same manner as described in Example 48. Its IR(KBr) spectrum showed absorptions at 2,930 (C_H, S), 2,870 (C_H, S), 1,635 (C=O, S), 1,435 (S), 1,250 (m), 1,205 (m) and 1,015 (m) cm_1; and ʹH NMR (HCO₂H, 60mHz): δ 0.72-1.46 (m, 4H, _CH2_), 1.52-2.37 (m, 4H, _CH₂CO_) and 2.70-3.69 (m, 8H, _NCH₂_).
- 1,4-Phenylenediacetonitri1e (0.312 g), hexamethylenediamine (0.232 g), RuH₂(PPh₃)₄ (0.069 g), water (0.074 g) and 1,2-dimethoxyethane (0.5 mℓ ) were reacted at 180°C in an argon gas atmosphere for 24 hours in a sealed tube. After the reaction, precipitates were separated by filtration, washed with chloroform and dried. A polyamide that did not melt at 300°C was obtained in a 93% yield. Its number average molecular weight was 14,000, which was calculated in the same manner as described in Example 48. Its IR(KBr) spectrum showed absorptions at 3,250 (N_H, m), 2,920 (C_H, s), 2,850 (C_H, m), 1,630 (C=O, s), 1,530 (N_H, m), 1,425 (m) and 740 (m) cm_1.
- As is clear from the foregoing Examples, the use of ruthenium, rhodium and molybdenum complexes according to the present invention enables amides to be efficiently prepared directly from nitriles, amines and water, in a single-step process, so that curtailment of reaction time, compaction of equipments and clean operations can be realised as compared with the conventional two-step process for amide synthesis. In particular, the advantage of the present invention lies in the fact that the reaction can be effected under neutral conditions with a small amount of water, which is economical in energy. Further, by using dinitriles and diamines, or aminonitriles according to the present invention, polyamides can be produced in a single-step manufacturing process.
Claims (19)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60044939A JPS61205221A (en) | 1985-03-08 | 1985-03-08 | New process for preparation of amide from nitrile and amine |
JP44939/85 | 1985-03-08 |
Publications (3)
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EP0197657A2 EP0197657A2 (en) | 1986-10-15 |
EP0197657A3 EP0197657A3 (en) | 1988-01-07 |
EP0197657B1 true EP0197657B1 (en) | 1991-02-27 |
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EP86301647A Expired EP0197657B1 (en) | 1985-03-08 | 1986-03-07 | A novel process for preparing amides from nitriles and amines |
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---|---|
US (2) | US4801748A (en) |
EP (1) | EP0197657B1 (en) |
JP (1) | JPS61205221A (en) |
CA (2) | CA1269392A (en) |
DE (1) | DE3677621D1 (en) |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS61205221A (en) * | 1985-03-08 | 1986-09-11 | Univ Osaka | New process for preparation of amide from nitrile and amine |
US5608108A (en) * | 1988-11-14 | 1997-03-04 | Sloan-Kettering Institute For Cancer Research | Potent inducers of terminal differentiation and method of use thereof |
US5055608A (en) * | 1988-11-14 | 1991-10-08 | Sloan-Kettering Institute For Cancer Research | Novel potent inducers of thermal differentiation and method of use thereof |
WO1991008191A1 (en) * | 1989-11-14 | 1991-06-13 | Sloan-Kettering Institute For Cancer Research | Novel potent inducers of terminal differentiation and method of use thereof |
WO1991000257A1 (en) * | 1989-06-30 | 1991-01-10 | The Trustees Of Columbia University In The City Of New York | Novel potent inducers of terminal differentiation and methods of use thereof |
US5700811A (en) * | 1991-10-04 | 1997-12-23 | Sloan-Kettering Institute For Cancer Research | Potent inducers of terminal differentiation and method of use thereof |
USRE38506E1 (en) | 1991-10-04 | 2004-04-20 | Sloan-Kettering Institute For Cancer Research | Potent inducers of terminal differentiation and methods of use thereof |
US5369108A (en) * | 1991-10-04 | 1994-11-29 | Sloan-Kettering Institute For Cancer Research | Potent inducers of terminal differentiation and methods of use thereof |
US5380946A (en) * | 1993-07-30 | 1995-01-10 | Monsanto Company | Process for preparing p-nitroaromatic amides and products thereof |
JP3429095B2 (en) * | 1994-05-27 | 2003-07-22 | ツイマー・アクチェンゲゼルシャフト | Process for producing polyamides based on α, ω-dinitrile |
JP3570990B2 (en) * | 1997-09-05 | 2004-09-29 | デュポン カナダ インコーポレイテッド | Manufacture of branched polyamide |
US6075117A (en) * | 1998-12-21 | 2000-06-13 | E.I. Dupont De Nemours & Company | Process for the hydrolysis of adiponitrile and the production of nylon 6,6 using dicarboxylic acids as the sole catalyst |
US6103863A (en) * | 1998-12-22 | 2000-08-15 | E. I. Dupont De Nemours & Company | Process for preparation of polyamide from dinitrile and diamine |
US6084056A (en) * | 1998-12-22 | 2000-07-04 | E. I. Dupont De Nemours & Company | Process for the hydrolysis of adiponitrile and the production of nylon 6,6 utilizing low catalyst levels |
EA200601252A1 (en) | 1999-09-08 | 2006-10-27 | Слоан-Кеттеринг Инститьют Фор Кэнсер Рисёч | A NEW CLASS OF SUBSTANCES CAUSING DIFFERENTIATION OF CELLS AND THAT HYSTONDE EDSYLASE INHIBITORS, AND METHODS OF THEIR APPLICATION |
US6509439B1 (en) | 2000-04-14 | 2003-01-21 | E. I. Du Pont De Nemours And Company | Process for the production of polyamides from dinitriles and diamines |
WO2004089293A2 (en) * | 2003-04-01 | 2004-10-21 | Memorial Sloan-Kettering Cancer Center | Hydroxamic acid compounds and methods of use thereof |
CN1304404C (en) * | 2005-07-08 | 2007-03-14 | 北京科技大学 | Nickel metal organic supermolecular compound and its synthesis method |
CN101263105B (en) * | 2005-09-16 | 2012-07-04 | 株式会社Lg生命科学 | Process for preparing beta-ketoester compounds |
CN102964195B (en) * | 2012-11-28 | 2015-06-24 | 温州大学 | Method for preparing second-level and third-level substituted amide |
CN104693059A (en) * | 2013-12-09 | 2015-06-10 | 中国科学院兰州化学物理研究所 | Crystal formation of CAHB (diacetyl hexamethylene diamine) differentiation-inducing agent as well as preparing method and application thereof |
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US2280578A (en) * | 1938-09-15 | 1942-04-21 | Du Pont | Amides of aliphatic polycarbothionic acids and their preparation |
US2421030A (en) * | 1945-09-10 | 1947-05-27 | Phillips Petroleum Co | Process for synthesis of amides |
US3040095A (en) * | 1960-07-13 | 1962-06-19 | Allied Chem | Hydrolysis of acetonitrile to acetamide |
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DE1768675B1 (en) * | 1967-06-16 | 1972-05-31 | Asahi Chemical Ind | Process for the catalytic production of N, N-dialkylamides |
US3670021A (en) * | 1967-12-14 | 1972-06-13 | Nat Distillers Chem Corp | Catalyzed hydrolysis of nitriles to amides |
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US3597481A (en) * | 1969-01-16 | 1971-08-03 | Dow Chemical Co | Heterogeneous catalyst for the liquid phase hydrolysis of nitriles to amides |
US4036879A (en) * | 1970-11-19 | 1977-07-19 | The Dow Chemical Company | Catalysts for the hydration of nitriles of amides |
US4329500A (en) * | 1970-11-19 | 1982-05-11 | The Dow Chemical Company | Catalysts for the hydration of nitriles to amides |
US3673250A (en) * | 1970-12-01 | 1972-06-27 | American Cyanamid Co | Catalytic hydration of nitriles to produce amides |
US3794682A (en) * | 1970-12-01 | 1974-02-26 | American Cyanamid Co | Hydration of nitriles |
JPS5132472B2 (en) * | 1971-08-25 | 1976-09-13 | ||
US3825596A (en) * | 1972-05-23 | 1974-07-23 | Showa Denko Kk | Process for preparation of n,n-dialkyl toluamide |
US3847876A (en) * | 1972-07-06 | 1974-11-12 | Halcon International Inc | Preparation of polyamides by polymerization of a dinitrile,a diamine and water in the presence of controlled amounts of ammonia |
US3948989A (en) * | 1974-06-12 | 1976-04-06 | Phillips Petroleum Company | N-monosubstituted amide production |
US4060553A (en) * | 1976-05-10 | 1977-11-29 | Petrolite Corporation | Hydroxyalkylaminoalkylamides and preparation and uses thereof |
US4380623A (en) * | 1981-04-03 | 1983-04-19 | Standard Oil Company | Preparation of polyamide from dinitrile, diamine, water, and CO2 catalyst |
US4554345A (en) * | 1981-04-03 | 1985-11-19 | The Standard Oil Company | Preparation of liquid polyamide from dinitrile and diamine |
US4436898A (en) * | 1982-04-20 | 1984-03-13 | Davy Mckee Aktiengesellschaft, Borsigalle | Preparation of spinnable polyamide from dinitrile, diamine, H2 O with P containing catalyst |
DE3128575C2 (en) * | 1981-07-20 | 1983-11-17 | Deutsche Texaco Ag, 2000 Hamburg | Process for the preparation of N, N'-disubstituted 3-aminopropanamides |
US4501881A (en) * | 1982-04-05 | 1985-02-26 | The Standard Oil Company | Preparation of polyamide by contacting diamine, dinitrile, water, dicarboxylic acid |
US4520190A (en) * | 1982-11-08 | 1985-05-28 | The Standard Oil Company | Preparation of polyamide from dinitrile, diamine and water with P catalyst |
US4490521A (en) * | 1983-10-11 | 1984-12-25 | The Standard Oil Company | Preparation of spinnable polyamide from dinitrile/diamine/water with metal salt of oxygenated phosphorus compound catalyst |
US4542205A (en) * | 1984-09-17 | 1985-09-17 | The Standard Oil Company | Process for the manufacture of polyamides utilizing a mixture of an oxygenated phosphorus compound and a molybdenum compound as catalyst |
US4543407A (en) * | 1984-12-03 | 1985-09-24 | The Standard Oil Company | Catalytic process for the manufacture of polyamides from diamines and diamides |
US4603192A (en) * | 1985-01-10 | 1986-07-29 | The Standard Oil Company | Process for the manufacture of spinnable polyamides utilizing a mixture of an oxygenated phosphorus compound and an oxygenated boron compound as catalyst |
JPS61205221A (en) * | 1985-03-08 | 1986-09-11 | Univ Osaka | New process for preparation of amide from nitrile and amine |
-
1985
- 1985-03-08 JP JP60044939A patent/JPS61205221A/en active Granted
-
1986
- 1986-03-07 DE DE8686301647T patent/DE3677621D1/en not_active Expired - Lifetime
- 1986-03-07 US US06/838,199 patent/US4801748A/en not_active Expired - Lifetime
- 1986-03-07 CA CA000503525A patent/CA1269392A/en not_active Expired
- 1986-03-07 EP EP86301647A patent/EP0197657B1/en not_active Expired
-
1987
- 1987-06-19 US US07/067,414 patent/US4942220A/en not_active Expired - Lifetime
-
1989
- 1989-10-19 CA CA000615533A patent/CA1280848C/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
EP0197657A3 (en) | 1988-01-07 |
JPS61205221A (en) | 1986-09-11 |
DE3677621D1 (en) | 1991-04-04 |
CA1269392A (en) | 1990-05-22 |
US4801748A (en) | 1989-01-31 |
JPS6233211B2 (en) | 1987-07-20 |
US4942220A (en) | 1990-07-17 |
CA1280848C (en) | 1991-02-26 |
EP0197657A2 (en) | 1986-10-15 |
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